Condensation product and method of preparing same.



AVALLABLE corr hurrah snares manna orricn.

LAWRENCE v. RED1VIAN,- or nvans'rgn, AND ARCHIE J. WEITH AND FRANK P.BROOK,

OF CHICAGO, ILLINOIS, ASSIGNORS TO REDMANOL CHEMICAL PRODUCTS COMPANY,OF CHICAGQILLINOIS. A CORPORATIQN OF WEST VIBGINIA.

CONDENSATION PRODUCT AND METHOD OF PREPARING SAME.

No Drawing.

1 b all whom it may concern: I

Be it known that We, Liuvanxcn MAN, a citizen of Canada, residing atEvanston, in the county of Cook and State of llllnois, and FRANK P.Bnocn and Ancillacondensation products of phenol'and subwe prepare afusible,

stances containing the methylene radical,

and methods for preparing the same.

The invention is in the nature ofan improvement upon the intention setforth and claimed in the patent of Lawrence V. Redman, No. 1,188,014,granted June 2Q, 1916.

. The invention is highly desirable for pro ducing a phenoliccondensation product for use as a molding compound, or for otherindustrial purposes, where a transparent product is not required; and,also, the invention may be very advantageously employed in the compound.

The primary object is to provide a process which will enable a substanceof this character to be produced on a commercial scale in an exceedinglysimple and very practical manner, the process beingof' such character asto' make the reactions involved, keep. the mass undergoing treatment insuch condition as to make it at all times readily handled, and alsoenable a compound of definite characteristics to be produced with thegreatest certainty and under conditions presenting greatpracticaladvant'ages.

directly combining a phenolic body, such as cresol, with an activemethylene body, such as hexalmethylenetetramin, by an anhydrousre-action carried on substantially in the absence of water, using anexcess of the cresol, r

the re-action being carried on ,with a relatively small percentage ofcreosote Oll present in the mixture, or the cresote 011 being introducedinto the fusible mass before pro- Spccification of Letters Patent.Application filed June 19, 1916. Serial No. 104,495.

where pigments are production of a, transparent readily controllable.

, oi? the heat the rapid evolution -erably 165 C. for

Patented Oct, 9, 1917.

ceeding to the final steps, which result in} compound capable of beingconverted to final infusib'le, insoluble product; and having obtained,by this simplefpreliminary step, What We term an initial fusible productof a character WlllCll'lS peculiarly adapted to further treatment, Weincorporate in 'oigmix with the resin a substance which will furnishsufficient methylene to convert the initial product, at a propertemperature, to a final insoluble, infus'ible, chemically inertsubstance which may be termed the final product. -The active methylenesubstance which maybe introduced atthis point is preferablyhexamethyleuetetramin; and desired, they are usually stirred into thefluid product at thesame stage at which the additionalhexamethyleenetetramin is introduced. a Y i f The process further involves thesubsequent mixing of the potentially rte-active resin, preferably afterit has been cooled and comminuted, with fillers, such as-asbestos, mica,flock, wood pulp, etc, and subsequent treatment to put the material intomerchantable form, or in a form enabling it to be readily used as 'amolding (compound, or'for other purposes. cf In accordance with thepreferred method, wefirst obtain afu'sible mass having as a largeconstituent a condensation product of a. phenolic body and an .activemethylene body in the following manner: i

FMiig 972 pounds cresol', OH) 140 pounds hexame'thylenetetramin ((Glfi),N, ,'-;'Z8 pcunds creosote oil heat the mixture in a vessel or still,While stirring, to a temperature of 140? CL; then turn matically rising)5! apply further heat after of ammonia ceases, cona temperature ofpref-,-- forty-eight hours, pour the mass into a mixer, such asapairit-niixer, (the mass being new at a temperature of from 95 C. to C.and havingthe con sistency of a stiff liquid, or tafiy; add to, .or w,stir into, the mass 120 poundsof hexa-f, methylenetetramin; m? or stirinto the niass at the same stage such-quantity of dies or tinuing theheat at and allow the"evolutionioflam- 90 i monia to proceed (thetemperature auto- In, accordance with the improved process, f

anhydrous mass by ng a finely granulated product. This prod BESTAvAitAenzco taining both free cresol and free. hexaunzthylenetetramln)in pans, comminute the material, then mix with fillers, roll themaiutlul under such conditions as to cause a i ea'lain amount ofre-action and the producmm of sheets having the appearance of i ivytarred paper; finally allow the sheets material to cool; then break orcourse [grind in a grinding-mill, then pulverize in :1 heater-mill, siftand blend, thus producu-t salable as a molding compound, and may bemolded in heated molds, where conwrsion to the final insoluble,infusible product takes place.

The mixture, or batch, referred to above, "HillllllS cresol andhexamethylenetetramin in lhe proportions of about 9 mols. of oreol to 1mol. of hexamethylenetetramin; and :xlieli the admixture ofhe'xamethylenetetnunin to the fusible mass,'we have .what

HI'QSPOIIdS with about mols. of cresol o 1 mol. ofhexamethylenetetramin. The amount of hexa-methylenetetramin added afterthe fusible mass is produced is approxuiately 10 per cent. of the weightof the original. batch.

The creosote oil-employed is a commercial l' eosote oil, preferablydistilling at a temperature of approximately 220 C. to 270 l As isknown, creosote oil is a mixture of yclic hydrocarbons, containing noreadily reactive groups. Such a mixture cannot be :h-ssignated bydefinite formula. The mixture may comprise, however, a number of r yclichydrocarbons, such as naphthalene (C H anthracene (G H etc. Preferably,the mixture is freefrom hydroxyl, ehlorin, or any readily re-activegroup. Gwiphor may .be used as a substitute for a: facilitates thesubsequent preparation of the,

potentially re-active fusible resin, and lloall remains incorporated inthe comound without detriment to the final product. birtpon thecontrary, imparting a desimhlexplgpticity in the molding operation and ahigher tenacity, both in the fusible I product (when allowed to cool)and in the final product.

After the initial heating operation, the fluid is amber to dark incolor; and after approximately forty-eight hours of heat treatment atapproximately 165 (3., the substance remains a dark amber liquid. Atemperature of from 125 C. to 210 (J. may be used. The length oftreatment will vary, depending upon the amount of material being treatedand the temperature employed.

At a temperature of 100 0., the material is a stiff liquid, or tally,and may be pulled or stretched, like tafiiy, becoming lighter in color,when subject to repeated stretching.

Any suitablefat or wax may be used with a view to preventing thematerial from sticking in the dies. Beeswax, stearin, stearic acid,paratiin, etc., are illustratipns.

For a batch such as stated, the operation of stirring in additionalamount of hexamethylenetetramin necessary to give the requiredproportions for converting to the final infusible product and thepigments usually require about fifteen minutes, the temperature beingmaintained at approximately 100 C. The material is poured, af-

ter this mixing operation, in somewhat the consistency of tar, intoshallow pans, and-allowed to cool. After coarse breaking, if de sired,the material may be more or less -mogeneity of texture andcharacteristics throughout the mass of the material.

The purpose last indicated is accomplished by throwing or feeding aquantity of the dry pulp-like mixture of materials on a pair ofrevolving rolls, which are disposed close together and geared to operateat any desired speed. The friction created by this operation causes thematerials to adhere to the rolls. Water may be circulated through therolls to prevent excessive heat. At intervals of a few minutes, thematerial is cut or peeled from the roll and fed and re-fed through therolls, which thus perform a thorough mixing and blending operation.

.In this operation, the heat developed is doubtlesssufiicient to causesome chemical re-action. It is desirable, however, to prevent the heatfrom becoming too great, both becau'se too much heat interferes with thefree Working of thewmaterials on the rolls.

-35 and t action toward the I a rolling operation of ment is stillinfluid condition 55 lacquer. or varnish.

masses.

and also because any advanced stage of refinal product 18 to be avoided.Usually two minutes for a batch of material thrown on the vrolls issuilicient to give the desired blend. The sheets of material are thencut from the rolls; cooled and passed into the rinding-mill and coarseground and thence through the beater-mill and finely ground, sifted andblended.

The material is now in suitable condition for use as a molding compound,.and may be, molded in heated molds, Where conversion to the finalproduct takes place.

Taken from the rolls as a sheet, the potentially re-active material maybe rolled "into uniform sheet or plate used for various purposes. Thematerial may be. heated to plastic condition in open or closed, dies,and may be cast or molded, as desired. The material, either before orafter the 'admixture of filler, may be used for insulatvmg purposes. Thesame may be said with 25.

respect to the use of the material for molding purposes. Various otheruses of the compound, either before or after the admixture of thefiller, Will occur to those skilled .in the art.

,fusib 404ml to 1 mol. of hexamethylenetetramin.

Subsequent to the elimination of the ammonia, some of the cresol, say 10per cent. of *the amount originally employed, may be removed from themass by blowing hot air Q through the mass. The creosote oil may thenbefadded or mixed with the mass While it operation of mixing-with themass'the necessary amount of hexamethylenetetramin 5 0 to eflectconversion to the final infusible product.

. The fusible mass maybe dissolved in the usual solvents, such asalkalis, acetone, or and may be used as a If desired, a certainpercentage of hexamethylenetetramin may be incorporated in the varnish,so that where a mixture ofsolvents,

the varnish or lacquer is subjected to a subsequent heat treatment,conversion to the final infusible product will take place.

In theillustrations given, a fusible'mass containing a condensationproduct is produced by an anhydrous re-action substantially in theabsence of Water, and without the usemf a catalyzer. A small amount ofform. and may be improved process that i 7 process the seriousdifiicultieswhi'ch h'z'ive' and prior to the of the variousWater'pre'se'nt in the crc'sol, "as an impurity, would not interferewith the practice of the process. Any suitable phenolic body may be usedfor producing the initial product.

lVieta para-cresol is cheap, as compared" with phenol proper, and may beused ivith most excellent results in the process herein described. Anybody which will readily'furuish the n cessary methylene group to producethe anhydrous productprovided it be of an anhydrouscharacter,'orsubstiihtially so. In each instance, we 811115105 10suitable active methylene effect (he conversion to the final 'nod'uctasubstance which will readily furnish the necessary methylene ((3H,) tocoinbin vith the fusible product and effect conversioirto the finalinfusiblc resin. The su'bstancc e'inployed for this purpose ispreferably an anhydrous active methylene bo(ly,"sucli as?hexamethylenctetrainin. Where 'thisfinatcrial is employed, thecomparatively small amount of ammonia present in *the'poten tiallyre-active resin or purely as which occur inconverting the substance tothe final state. i

It will be noted as characteristic 'ofithe' {the 5s p. lith so long beenexperienced in this ai t by lie practice of the oldwetformaldehydeprocess with the attendant difficulties incidentto the"use of large quantities of water andne'cessarycatalyzers during thisstage of'prodiio" lnga phenolic condensation product, are

entirely obviated, and the resin, with ithe creosote oil incorporatedtherein, is left in such a desirable mobile state easy the succeedingillustration, a mo ding product capable being converted, i'

to the final infusible state.

steps in producing,"

as to'frender i a mixture will? an aid in expediting the re-actibiisllOthe molding operation, 7

Not onlyfso,

but the methodiollowed renders it possible to eliminate the ammonia inthe easiest pos; sible manner and to enable the condensation to becarried to a desirable advanced stage, prior to adding the fillers andthe 1neth lenes necessary to effect the final conver;

sion. The result or" the process isto produce a molding compound whichcan be quickly,

iis

converted to the final infusible statein the molding operation, thusexpediting the ivorli manufacturers who'use' the 120..

molding compound, which in, itself highly desirable result. Material [orthis character may be molded into'compara'tively large pieces andconverted to the final state Within a period of approximately fiveminutes; and the molded product possesses a high tensile strength,'whichobviates danger of breakage. It is characteristic of the efi'ect ofcreosote oil to greatly increase the tensile strength of the product. p.Itmill be understood that the proportions or any desired purpose.

suitable commercially obtainable phenolic body may be used.

" In the practice of the process, the ampnia evolved may be collectedand used For instance, the ammonia may be discharged 'into a solution offormaldehyde to produce fresh hexamethylenetetramm, and this, in turn,may

be used in ,the practice of the process.

- standing only,

Various variations in the details of the process are desirable,depending upon the' exact character'of theproduct desired, as will beunderstood from the foregoing explanation; The foregoing detaileddescription has been given for clearness of underand no unnecessarylimitation should be understood therefrom, but the appended claimsshould be construedas broadly as permissible in view of the prior art.

What we regard as new and desire to secure by Letters Patent is- 1. Inthe process of producing a phenolic condensation product, the ste :WhlChconsists in mixing a phenolic bo y and an active methylene body in theproportions of considerably more than one phenolic group to each activemethylene group of the methylene body, applying heat to produce afusible resin, an incorporating in the fusible mass a cyclic compoundhaving no readily re-active group. j

2. In the process of producing a phenolic" condensation product, thestepwhich consists in mixing a phenolic body and an active methylenebody in the proportions of considerably more than' one phenolic group toeach active methylene group of" the methylene body, incorporating 1n themixture a relatively small amount of a cygclic hydrocarbon, andsubjecting the mix ture to the action of heat to produce a fusi bleresin.

3. In the process of producing a phenolic condensation product, the stepwhich consists in mixing a phenolicbody and an active methylene body inthe proportions of considerably more than one phenolic oup to each actie methylene group 0 the methylene betly, incorporating in the mixture arelatively small amount of a mixture of cyclic hydrocarbon having noreadily reactive groups, and subjecting the mixture to the action ofheat to produce a fusible resin.

4. In the process ofproducing a phenolic condensation product, the stepwhich consists 1n mixm a phenolic body and a methyleneamin bo y in theproportionsof considerably more than one phenolicg-group to each activemethylene group of the aeth lene body, and also mlxing therewith acyclic hydrocarbon, and sub ecting said'hmixture to the action of heatfor a prolonged period to eliminate the ammonia and produce a fusibleproduct.

5. In the process of producing a phenolic condensation product, the stepwhich consists in producing an anhydrous reaction, substantially in theabsence of water, between a phenolic body and a methylene-amin body inthe proportions of-considerably more than one phenolic group to eachactive methylene group of the methylene body, such re-action beingcarried on, and the nitrogen expelled in the form of ammonia in thepresence of a cyclic hydrocarbon in the mixture.

6. In the process of producing a phenolic condensation product, the stepwhich consists in a phenolic body and a methyleneamin bo y inproportions of considerably more than one phenolic group to each activemethylene group of the methylene body, and creosote oi in relativelysmall proportion; and subjecting the mixture to the action of heat toexpel the nitrogen in the 'form of ammonia.

7. In the process of producing a phenolic condensation product, the stepwhich consists in mixin' a phenolic bodyand a methylene- 5 b0 y inproportions of considerably more than one phenolic group to each activemethylene group of the methylene body, and

creosote Oll in relatively small proportion;

substantially in the absence of water and causing an anhydrous re-actionto produce a fusible mass.

8. In the process of producing a phenolic resin, the step which consistsin mixing 3/ 5 phenolic body and a methylene-amin .body

in the proportions of substantially one and one-half mols. of thephenolic body to one mol. of the methylene-amin body, incorporating inthe mixture a relatively small proportion of acyclic hydrocarbon, andsubjecting the mixture to the-action of heat to eliminate the nitrogenin the form of am- 11101113.. (j

9. In the process of producing a phenolic resin, the step which consistsin'mixlng a phenolic body and hexamethylenetetramin in the proportionsof substantially one and oiie-half mols. of the phenolic body to onemol. of the hexamethylenetetramin, incorporatmg 1n the mixture arelatively small proportion. of creosote oil, and subjecting thermixturetothe action of heat to eliminate nitrogen in the form of ammonia. f i

10. the process of producing a phenolic 5 condensation roduct,'.the stepwhich consists a p enolic body and hexamethyla 1enetetramjn in theroportions ofi' substantiallyzozie and one-ha f mols. of the phenolic}ady .;m m L hw et ylene a minl an,

amount approximating one-half of the hexamethylenetetraniin, ing themixture to the actionjo'f elimination; of the nitrogen.

11. Therp'rocessof new @1 5 sist's in combining a methylene-alum bodyWither. phenolic body in the presence, of .a-- the materials being used10 cyclic hydrocarbon, in'the proportions ofconsiderablymore than onephenolic group of the phenolic, body to one methylene group "ofthemethylene-amin y; of and then incorporating stance containin'g'activemethylene in 'suiiicient quantity to efi'ect conversion of the compoundto a final insoluble infusible' state.

12. The re-actiye condensation sists" in combining a with a. phenolicbod cyclic hydrocarbon, in the proportions oomp'oundiwhichconjinethylene-an n body the materials being used one. methylene group:of the body; subjecting the mixture to the actionv of heat g-to museelimination. of nitrogen; and, then incofporating a filler and asubstance containing methylene in s'uflicient quantity to effectconversion of thecoin pound toa final insoluble5'infusible state. 13.The process'ofpt oducing a potentially reactive: phenoliccondensatio'ncompound, I which consists in combining hexarnethylenc- .tetramin'With-aphenolicbody by an anhy rous reeaction -in substantially the absence ofWater, 1 and inj the presence of a L cyclic hyd'rocarbo11 ,1 *the Imaterials 'eing ,.used in the proportionsof considerably more than onephenolic group ,to one methylene group, the -substance being'i'l'iiti'ally grceisulilicient tocause automatic heating of the mass,to "takeplace and suiticicntheat being applied to cause the climinatiohof thenitrogen in? the form of ammonia; and then introducing. afillercontaining imcthylcne in sufficient quantity to effect conversion, underheat, to the. final. insoluble, infusiblestate. 1i. The-processot'pioducing apotentially e-active fusible compound. which :consists in.combining a inethylcneamin body with a phenoIiobodmby an anhydrousreaction in substantialtlyctbc absence of Water and in the presence. ofcreosote oil. the materials 1 being-"used in' thc q'iropor'lzions ofconsider ably more than one 1 phenolic group of, the phenolic body toone methylene group of the metbyleucwaminbody, the mixture being initially subjected to-snch heat treatment as to cause the-;.expulsion;ofthc' nititogcn in the, -form of ammonia; thef incorporating in 65 thefusible'rcsin thusp: incedaisubstan'ce t .ii ht t ndsubject f y i p y,ie p ic ion of further. heat;

producing a potentially re-active. condensat on compound, which cons,

subjecting themixture to the action heat to cause elimination oflnitrogenq.

process of producing a potentially in the presence of a ofconsiderably'inore than I onephenolicgroup 0f the phenolicebody tomethylene-aniin tively small proportion fem-pointing in the fusi ,-conta1n1n;: methylene heated to a 'deand a substance.

the application of fusible state; then cool i ng and comminuting'thcpotentially i'e-actn'e resin, introducing a ment to fuse; filleras'a' constituent part-ofa bodyformed bfthe materials.

containing methylene in suificient gum -comp l the fin insoluble;inf-uslble'} state y 155 The sprocessmf producing ti :1 l ly' reflectivefusible com ound; "WllIClTCOH sists in (-ombininga methylencanninbodywith a; phenolic bodyyby an anhydrousre seamen substantially the*absc'nce of Tia an: andinthe prcsenceotcreosote oilfth; I materialsbeing used in tl'le -propoi tionsoi" considerably more than one phenolicgroup of the phenolic bodyto one nethylene groupi of the methylene-21minbody, the inixtuife being initially subjected to such .heat tr'ea t Iment as itoj cause the expulsion of the; nitrogenin the form of ammoniagthen in? troducinginto the fusible'niass a fillcrand a substancecontaining methylene in suffi cient quantity to effect 'coniersion' ofthe i' esin to a final insoluble, infusible condition, under theapplicationof'heat. i I 16. The process of producing a. poten tiallyie-actii'e'phonolic condensation prodnot, which consists inconlbininga'mcthyl' eneramin body with a phenolic body bya n anhydrousreaction in substantially the ab 'sen'ceof water and in= the'presence ofa rela of a cyclic hydro carbon. the mixture of niateI'iaIsbeing-SubQ pjectcd to the action ofheat to eliminate the nitrogen in the, form ofammonia; then-in" ble mass a substance) in suliicien-t quantity toeffect conversion to afinal insoluble .1

v fusible stateythen coolingand coinn inu'ting i i the potentiallyreactive resin. 17. The! process of producing a "potcn tiallyi'eactivcphenolic condensation p1'od-- not, which consists in combininga methyl-ienc-amin.bo lyovith a phenolic body by an anhydrous rc-actioninsubstantial lythc ab scnceof Water and in the presenceof a rela-v tivelysmall proportion of acyclichydrocarbon, the mixture of materialsbcingsubjected to the actionot' heat to eliminate the J nitrogen in the formof'am'monia; then incorporating'in the fusil'ilcnmss' a substancecontaining methylene in sufficient quantity to effect conversion to afinal insolublepinelien, and subjbcting to mechanical treat the res nand" incorporate the i 18. 'l he, process of producing. a po'ten- 1tially reactive phenolic condensation compound. which consists incombining amethyl' a one body With a phenolicbody in the prosonce of acyclic l vdrocarbon;the materials" boing'used; in the proportions ,or'consideb' ably more than one phenolic"groupof'the phenolic hody tooneinethylcnegroup of themcthylene body, and the oyclic-hydro-- 3,

carbon being used in"r elatively small propdrtion, the substance, beingsubjected to the action of heat to produce a fusible resin; thenintroducing a substance containing methylene in suihcient quantity toefiect con- Version of the fusible mass to the final ill-: soluble,infusible state;'then cooling and comminuting the mass;'-thenam1xmgw1th'the comminutcd mass afiller; and then subjecting the mass to mechanicalaction under a fusing temperature and efiecting blending andincorporation of the filler as an integral portion of the fusible body.

19. The process of producing a potentially re-active phenoliccondensation compound, which consists in combining a methylene body witha phenolic body in the presence of a cyclic hydrocarbon, the-materialsbeing used in the proportions of considerably more than one phenolicgroup of the phenolic body to one'methylene group of the methylene body,and the cyclic hydrocarbon being used in relatively small proportion,the substance being subjected to the action of heat toproduce a fusible,potentially reactive resin then introducing a substance containingmethylene in suflicient quantity to effect conversion of the fusiblemass to the .final insoluble, infusible state; then cooling andincorporation of the filler as antintegral portion ofthe fusible body;and finely com minuting the mass and sitting the comminuted materials,thus attaining a granular, potentially reactive product.

i 20. The process of producing a poten' tially re-active compound, whichconsists in combining a methylcneamin body with a phenolic body by ananhydrous re-action in substantially the absence of Water and in thepresence of a relatively small proportion of creosote oil, the phenolicbody'and methylene-amin body being used in the proportions ofsubstantially one and one-half phenolic groups to one methylene group,the substance being subjected to the action of heat to eliminate thenitrogen; incorporating in the fusible mass thus produced a substancecontaining methylene in suflicient quantity to effect conversion to afinal in soluble, infusible state; cooling and comminuting the mass, andintroducing a filler; then fusing and blending the mass.

21. The process of producing a potentially re-active compound, whichconsists in combining a methylone-amin body with a phenolic body by ananhydrous reaction in substantially the absence of water and in thepresence of a relatively small proportion of creosote oil, the phenolicbody and methylene-amin body being used in the proportions ofsubstantially one and one-half stance containing methylene in suflicientvquantity to effect conversion to a final he soluble, infusible state;cooling and commi nuting the 'mass and introducing a filler;

fusing and blending the mass; then; com- I minuting the material thusproduced;

22. The 'process of producing a' potentially re-active phenoliccbndensation. product, which consists in combining hexameth"ylenetetramin with a phenolic'body by an.

anhydrous re-action insubstantially the absence of water and in thepresence of a relatively small proportion of a cyclic com-- pound, thephenolic body and hexamethylenetetramin being used in the proportions"of substantially one and one-half phenolic groups ,to one methylenegroup, the mixturebeing subjected to the action of ,heatr to. eliminatenitrogen; then incorporating in t the fusible-mass thus produced amethyleneamin body containing methylene in suiiicien't quantity toeffect conversion to alinal infusible state; then mechanicallyfusing-sand blending the materials.

23. In the process of producing a potentially reactive phenoliccondensation product, the step which consists in mixing with a fusiblephenolic condensation product containing an excess of phenolic body, asubstance containing methylene in sufficient quantity to effectconversion to an infusible st rte; then cooling and comminuting themiss; then incorporating a filler; then subjezting the mass to theaction of rolls to mechanically fuse and blend the mass.

524. In the process of producing a potentially ie-active phenoliccondensation prod not, the step which consists in mixing a fusiblephenolic condensation product containing an excess of phenolic body anda relatively small percentage of a cyclic compound, a substancecontaining methylene in sullicienh' quantity to efi'ect convcrsion to aninfusible state; then cooling and .comminuting the mass; then subjectingthe mass to the action of rolls to mechanically fuse and blend the mass.i

25. As a new composition of matter,'thc

fusible anhydrous resinous, condensation a phenolic body in proportionsfurnishingconsiderably more than one phenolic group to one activemethylene group, and incorporating 1n the mass a relatively smallproportion by weight of said mixture of cyclic hydrocarbons.

if hydrous re action, substantially in'th'e ab sence 'of Water, 'a'methylene-amin. body and.

a phenolic-body iii-proportions furnishing r substantially "one andone-half, phe'milic l groups toone active methylene'group, suchre-action carried on ini the presence of a relativelysinallproportion-by weight of a cyclic hydrocarbonin the'mixture,

7.'As a new composition of' matter,- a'

potentially re-ac'tivve fusible j phenolic condensation vproduct,produced by combining a phenolic body one-half phenolic groups to onemethylene group, incorporating creosote oil' in the compound,subsequently mixing with-the compound a methylenesubstance containingsuflicient methylene to eflect conversion to a.

final infusible state 'm1nutingthe mass. v .28. As a new composition ofmatter, a

fusible phenolic condensation product, produced by combining a aphenolic body then and com:

potentially re-active and an active -1nethylene body n proportions ofsubstantially one and one-half phenolic groupstoonemethylene a0 group,incorporatmg' creosote oil in the compound; subsequently. mixing'withthe compound a methylene substance containing,

sufficient methylene to efiect conversion to a final'in fusible state;cooling and" comminuting the mass; then mixing a filler 'vvith thecomlninuted mass; andthen fusing,

anhydrous resinous condensation" and blending, ivi-thout converting tothe final" infusible state. 3

densation product, produced by anhydrous reaction between asubstantially anhydrous methylene body and a substantially anhydrousphenolic body and having incorpo- "rateditherein acyclic hydrocarbonhaving r .30 moldedproduct comprising a phe: nolic condensation product,produced by ana methylene-amin anhydrous phef nolic body andhavinglIICOIPOI'atBdjthGIGlH and an" active methylene body in proportionsofsubstantially one and noireadily re-active group.

hydrous reaction between v body" and a substantially moldedproductcomprising a cone a a a cyclic hydrocarbon in relatively small pro-.portio'ns and possessing no readily, re-active group. r p l 31. A'nolded hydrous reaction between porated therein arelatively smallpr0por-.- I

tion,of creos'ote oil.. I 1 y 33. A molded product comprising apheporatetl f therein a" small proportionof creosote oil.

LAWRENCE-V. REDMAN.

ARCHIE J. WEI'TH. FRANKVP. BROOK.

product comprising a phejnoliccondensation product, produced by anamethylene-amin body .and .asubstantially anhydrous phe-- i 607 it ctcomprisinga phenolic condensation product having incorfiller and arelatively r a

